Organic compounds and methods of preparing same



Patented l7 1948 ORGANIC COltflOUNDS AND METHODS OF PREPARING SAMEDwight James Potter, Allendale, N. 3., assignor toColgate-Palmolive-Peet Company, Jersey City, N. .I., a corporation ofDelaware No Drawing. Application April 24, 1942, Serial No. 440,390

15 Claims. (01. coo-sin The present invention relates to a process ofproducing novel organic sulphur compounds and,

more articularly, to a process of producing organic sulphur compoundshaving valuable detergent and foaming properties, and tothe novelproduct of said process.

It is an object of the present invention toprovide a novel process forpreparing valuable detergent compositions.

It is another object of this invention to provide a novel process forpreparing organic sulphur' compounds from relatively inexpensive organicmaterials by reacting .said materials with a halogen derivative of aloweroxidation product of sulphur in the presence free radicals.

.It is also an object of the invention to provide a new and inexpensiveprocess for preparing organic sulphinate and/or sulphonate salts from;

organic materials, including saturated hydrocarbons obtained frompetroleum oils.

The present invention also contemplates the series of equations aresuggested as a possible explanation of the reaction mechanism, althoughit will 'be understood that the present disclosure is neither boundthereby nor limited thereto Equation .1 indicates the dissociation ofchlorine into two electrically neutral chlorine atoms or free radicals.Equation '2 represents the reaction of a chlorine atom or free radicalupon an organic provision of a simple and inexpensive method for makingorganic sulphinio acids and derivatives thereof for use in variouschemical syntheses,

It is also within the contemplation of this invention to provide novelorganic sulphinic acids and sulphinates and derivatives thereof,

The invention further provides novel organic sulphur compounds havingvaluable detergent, emulsifying and wetting properties.

Other objects and advantages of the invention will be apparent from thefollowing description. According to the. present invention, organiccompounds are'reacted with a halogen derivative of a lower oxidationproduct of sulphur, such as the thionyl halides, and a compound capableof providing a free radical, that is, a particle having an unpairedvalence electron, such as a halogen in the presence of actinic light,toiorm organic sulphur compounds, such as organic sulphinyl halides.Unreacted and by-pmduct gaseous materials are then preferably removed.and the product is hydrolyzed with an alkaline agent and may optionallyb oxidized to yield a sulphonate. If desired, t e product may be reactedwith other organic compounds to form secondary derivatives.

Although the mechanism of the reaction is not thoroughly understood, itis believed that the presence of a free radical, such as a nascentchlorine atom, acts upon the organic compound to strip off a hydrogenatom, forming hydrogen chloride, and to leave the organic residue as afree radical available for reaction with the organic sulphur compound.Thus, the following compound, wherein It represents an alkyl orsubstituted alkyl group linked to hydrogen. According to this suggestedreaction mechanism, the chlorine atom splits the hydrocarbon molecule toform. hydrogen chloride and to leave an alkyl or substituted alkyl freeradical. carbon radical is thus available for reaction with thionylchloride or other halogen derivative of a lower oxidation product ofsulphur, and, as shown in Equation 3, an organic sulphinyl chloride anda free chlorine atom are produced. The

free chlorine atom thus produced is then available for opening upanother molecule of the organic compound for sulphlnation. If weconsider only Equations 2 and 3, it would appear that chlorine servesmerely as a catalyst in the reac:

'tion. However, the chlorine atom may react with 80 a hydrocarbon freeradical, as formed according to Equation 2, to produce a chlorinesubstituted organic compound, such as an alkyl chloride. and thus beremoved from the cycle of the reaction.

It will be-appreciated that this theory of reaction is not necessary toan understanding of the present inventiomas disclosed herein, and thatthe same is advanced merely as an aid to the further development of theart.

When employing a thlonyl halide as the reactant, a sulphinyl halide ofth organic compound is formed. This product can then be hydrolyzed toyield a sulphinic acid or it may be hydrolyzed and neutralized toproduce a salt thereof. The sulphination product, whether sulphinylhalide, sulphinic acid or sulphinate, can also be oxidized to thecorresponding sulphonation product. The unoxidized product is soluble inalkali, but may separate out when the solution is acidified, where,

upon it can be partially redissolved in alkali. Even in dilutesolutions, the product shows unusual foaming, washing and wettingpowers.

'In selecting organic compounds for treatment according to the processof this'invention, it is preferred to use aliphatic hydrocarbons of anydesired number of carbon atoms to the molecule,

The free hydroorganic compounds can also I and 01 iuriuryl. alcohol,iuriural,

- s to mix thionyl chloride therewith and to chlorine vapors into said wure in veryiinely dispersed state in the presence of actinic rays.Satisfactory detergent compounds have been pre pared from straight chainhydrocarbons having about 8 to about 26 and preferably about 12 to about20, carbon atoms to the molecule. Cycloalkanes, alcohols, iatty acids,and other aliphatic be sulphinated by this process. g

The molar proportion of the organic compound to either thehalogenderivative oi thelower oxinishing the free radical may be widelyvaried, as desired. However, when employing a thionyl halide and ahalogen as thetreating materials, as it is generally preferredto'halogenate a amount oi. the organic compound, it has been foundadvantageous I proportion of thionyl halide and to provide about 2 toabout}: mole of of organic material and, conversely, to use only organiccompound,

The treatment with minimum thionyl halide for each .mol-J:

. stannic chloride, liquid hydrogen enraeoe (methyl cyanide),dlchlordiethyl ether, trimethyif chloriormate, phosgene,

amine, trichlormethyl fluoride, liquid hydrogen chloride, borontrifluoride dlhydrate, nitrobenzene, i-nitropropane, 2-nitropropane,cresol, sulphur monochloride and various miscible mixtures or theforegoing solvents, the last flve named being more eilective when usedat fill hinyl halides'to dation product of sulphur or the compound furtoexcecdthe stolchiometri'c, 7

I about-0.2 to about 0.5 mol oi halogen per mol of thionylis preferablycarried out withthionyl'chloride and chlorine at C. and about requiredfor the 100 C. and for a length of time n r ues-1 h materials t sum rrsror this temperature range or higher,,it is-advantageous to operate undersuperatmospheric pressure. or to reflux. Although it is preferred. touse chlorine and thionyl'chloride as treating agents, .thehalogen used.may also be fluorine,

desired degree of sulphination halogenation or the organic material."

a temperature between about addition of an adluvant solvent or solventsimlow temperatures.

, the heating to remove thionyl halide.

0! these solvents. some, such as the nitro compounds, have a slightoxidizing eflect and thus tend to oxidize certain organic sulphonylhalides; this tendency may or may not be of advantage, depending uponwhether organic sulphonates or sulphinates are desired. The use ofalcohols as preferential solvents, as disclosed supra, may cause theesteriiication or the sulphinyl halides,.but, except for possibleloss-oi alcohol thereby in the succeeding hydrolysis, the subsequentoperations are not atrected to any disadvantageous extent. when usingsome or the aforementioned compounds, such as the alcohols or acids, asselective solvents for the sulphinyl halides, it is desirable .to havethe reaction mixture. substantially tree of thionyl halide beforeextracting in order to avoid side reactions. With most of the solventsdisclosed, extraction may be carriedout beioreor after The organicsulphinyl halides may be extracted with a preferential solvent. with orwithout the miscible or only slightly miscible with the pro!- erentialsolvent. Liquid alkanes or low molecuiodine orbromine, and thethionylhalide may be a fluoride or/bromide'. Selenious or tellurous oxyhalidesmay replace the thionyl halide (sulphurous ox'yhalide) as a reactant,and the corresponding oxyc rides, oxybromides and oxyiiuorides areapplicable for this purpose. The

halogen may be replaced by other compounds capable 01! providing freeradicals, such as lead alkyls under thermal decomposition, etc,

The sulphination product may be freed from unreacted material by heatingto between about 100.and about 125 C. to remove gaseous reactants, andknown methods, including fractional distillation, iractionalcrystallization, extraction and other separation procedures or anycombination of these, may be employed for separat ing theproduct fromnon-gaseous reactants and organic sulphinyl halides with a selectivesolvent. ior separating them from unreacted hydrocarbons and/orhydrocarbon-like materials and from merely halogenated derivativesthereoi. The organic sulphinyl halides are relatively soluble insolvents ior polar compounds, whereas the unreacted or merelyhalogenated materials are insoluble or sparingly soluble therein.

Among the solvents which may be employed as preferential solvents inextracting the sulphination product from the reaction mixture are liquidI impurities. 'A preferred method is to extract the la! weight, such aspropane, butane, pentane. hexane. heptane. octanemonane, and petroleumether, and other su ntially non-polar solvents and mixtures thereof maybe added to the reaction mixture as adiuvant solvents. in thisconnection before, after and/or simultaneously with the organicsulphinyl halides thereafter. sep-' arated from the preferential solventare substantially pure and consequently more desirable because of theunimpaired detergent properties of the sulphinates and/or sulphonatesderived therefrom. The low-boilin solvents, such as methyl formate orliquid sulphur dioxide, may

sulphur dioxide, liquid carbon dioxide, nitroalhanesincludingnitromethane and nitroethane.

dry ethyl alcohol, wet methyl alcohol, pyridine,

slycolchlorhydrin, glycerol chlorhydrin, glycol, glycerol, dlmethylsulphate, diethyl sulphate, dibutyl sulphate, phemonoformate, glycol 3ml, methyl iormate, glycol diiormate, ethyl tormate, formic acid, methylacetate, glycol monoacetate, glycerol monoacetote, acetic acid, aceticanhydride, aoetonltrile be readily separated from the'organic sulphinylhalides by vaporization and, may be condensed and reused for treatmentof additional material or tor any other purpose.

A preferred extraction procedure maybe periormed by adding about anequal volume of an oxygen-containing preferential solvent for the polarsulphinyl halides, such as methyl formats or liquid sulphur dioxide, tothe organic sulphinyl halide reaction mixture and then an equal volumeof immiscible non-polar solvent. such as hexane. The order of adding thesolvents may be reversed, or they may be used simultaneously. Themixture separates sharply into two liquid phases. One or the phasesconsists mainly of polar solvent and contains the major portion 01' theorganic sulphinyl halide, and the other phase contains the non-polarsolvent solution of hydrocarbon-like material and halogenatedderivatives thereof. The oxygenated solvent layer, e. g., liquid sulphurdioxide, is usually more dense than the non-polar solvent layer, e. g.,hexane; hence, the latter forms the upper layer. It is desirablet'o'i'orrn layers having widely different specific gravities in order topromote separation. Either solvent may be replaced by substantiallymiscible mixed solvents performing in a manner substantially similar tothe solvent replaced.

The polar solvent formate or liquid sulphur dioxide layer, may beseparated by known methods, such as drawing 4 The organic sulphinylhalides are preferably recovered from the selective .solvent by removalof the solvent in gaseous form.v Thus, the removal of solvents having alowboiling point may be accomplished by bubbling an inert gas such,

nitrogen, stack gases,- etc., through the mixture and/or .by' gentleheating.

as carbon dioxide,

and/or byother means. Suitable equipment may be provided for carryingoutthese operations,

phase, such as the methyl oil, decantation, centrifuging or the like,and

reactive with thepreferential solvent for the sulphinyl halides underthe, reaction conditions, will assist in removing nonesulphonatedmaterials, 'e.'g.', aromatics, olefins and the like, which are somewhatsolublein the, liquid sulphur dioxide or 1 other polar solvent. but thanthe sulphinyl halides.

Continuous extraction procedures. as by dilution of the mixturewith onesolvent and countercurrent washing withthe other solvent, may beeffectively and economically carried out. It is also contemplated thatone or more preferential single or multiple contact; countercurrentmultiple contact, and continuous countercurrent contact. -Using eitherof the two last mentioned, backwash or reflux operation is preferablyemployed to obtain thorough extraction. Itis even possible to conductthe continuous extraction procedure simultaneously with the formation ofsulphinyl halides, although this may be undesirable where the solvent orsolvents employed enter into reaction with the starting materials orproducts under the reaction conditions. The extraction of the impuresulphinyl halide product can be conducted in several stages wherein themixture is first extracted with one solvent and the rafllnate thereofextracted with the second solvent, or the solvent-free extract from thefirst stage of extraction maybe re-extracted with a second solvent. Thissolvent; may be recovered from the extract and/or the rafllnate byextraction with a suitable secondary solvent therefor. Extraction with asecondary solvent of relatively low boiling point is particularlydesirable in those cases where the primary extractant is high-boiling.The solvents may be recovered directly from the extract, from theraflinates or from the secondary solvents by ing distillation, ing-outor the like. The recovered solvents may then be reused forfreshmaterials.

anysuitable method, includse the solubility of the organic evaporation,crystallization, salt which are less polar solvents, such as liquidsulphur dioxide with an i whereby the volatility of the low-boilingsolvent,

such as liquid sulphur dioxide, may be increased,

as by reducing the pressurein the system. Such equipment may also beprovided with condensing means, whereby the volatilized sulphur dioxideand/or other solvents employed may be recovered for reuse.

The sulphinyl halide product, thus .freed by extraction or otherwisefrom unreacted material and impurities, may then be hydrolyzed withwateror with aqueous solutions oi' alts and/or acids or alkalies, andpreferably with an alkaline agent, such as a caustic solution. The useof an alkaline agent permits neutralization along with hydrolysis.Excess gaseous reactants, by-product and/or other gaseous material,ifstillspresent, may be removed from the sulphin'ation prodnot, beforeor after hydrolysis, by blowing with" substantially inert gases, such anitrogen, carbon dioxide, sulphur dioxide, flue gases and/or steam.

Air or other oxygen-containing gasmay be similarly employed, where theproduct is ultimately to be oxidized to the sulphonate.

.tinued' until no more time the organic solvent is the only liquid whichThe hydrolyzed product may be extractedwith ether, gasoline or the liketo remove any residual organic unsaponiilable materialtherefrom.Inorganic salts added or formed during hydrolysis and/or neutralizationmay be removed by extraction of the product with ethyl alcohol, butylalcohol and the like, or the solution may be dialyzed to obtain thisresult. Since certain inorganic salts which may be present, such assodium chloride, are soluble to ,anappreciable extent in these solvents,the hydrolyzed products may be purified by adding an amount of awater-immiscible organic solvent, such as benzol, toluol, or the xylols,capable of dissolving the salts of the organic sulphur compounds in theanhydrous state, but incapable of dissolving appreciable amounts oftheinorganic salts. The mixture is heated to boiling to vaporize boththe water and the organic solvent,'and the vapors are condensed andseparated. Inthis manner. the water can be removed from the condensate,while the waterimmiscible solvent is permitted to flow back into theboiling mixture. Reflux distillation is conwater separates, at whichremains in the distillation vessel. The organic solvent containing theorganic sulphur compounds in solution therein is then separated from theundissolved inorganic salts by filtration, decantation, and/orcentrifuging or the like, and the solvent is thereafter removed by knownmethods.

. While the reaction broad temperature limits, such as from about 10 C.and below to about 200" C. and above, it .is advantageous to conduct thesulphinatlon between about 25? preferred temperature rangemay beeffected by applying suitable controls, depending upon the.

Thus, the

rate of reaction and the heat evolved. reactants, diluents and/or vaporsmay be preheated cooling of may be carried out between c. and about 0.The' or precooled, the admixed liquids may be 7 vaporized, and/orexternal heating or actants.

liquid at the may then be continuously drolysis, to form sulphonicphenols, alcohols, aromatic hydrocarbons derivatives thereof,beta-keto-esters and other industrial chemicals. V

In preparing the valuable detergents and foamto thionyl halide to termalkyl halides and/9pm.

at higher temperatures. In such cases, temperature control is veryimportant in the production of materials of uniform properties.

The sulphination reaction is affected by many factors,includingtheconcentration of the reperature, the pressure,

ins treated, and the type and intensity of illumination or radiationemployed to catalyse the reaction. Lightrays from that portion of thespectrum extending fromthe blue to the ultraviolet are particularlyeflective in assisting the reaction.

The process may be continuously carried out, preferably by continuouslypassing the organic material to be illuminated vessel'in countercurrentflow to a heated rising gas mixture including the thionyl halide andhalogen. If the thionyl halide is a particular temperature employed. itmay be passed downwardly in concurrentnow with the organic material.Similarly, if theorganic material is in the gaseous state, it may bepassed upwardly in contact with the other reactants. The reaction ispreferably carried out in a tower capable of transmitting light, such asrings, beads, bubble plates, fibers, and/or various other shapes ofglass, plastic, rused silica, quartz and other llke..materials; Thesulphinated product moved from the bottom of the tower and may becontinuously or intermittently hydrolyzed and purified. Where a solventor solvents are used to extract the reaction product, these may beintroduced into the top of thetower along with the reactants, .asaforesaid,lf desired.

The sulphination products termed are readily susceptible to oxidation,especially after hyacids or sulphonic acid derivatives. The oxidationmay be accomplished by any of a variety of means, with or by-productsand/or other gaseous material by blowing, described supra. Otheroxidizing agents,

the time of treatment, the reaction tem-' the organic materials be-' orintermittently from about 12 to about so carbon atoms, and" sulphinateddownwardly in an containing a column of inert material without oxidationcatalysts. A convenient methother oxygen-containing r including nitricacid, the oxides of nitrogen, hy

drogen peroxide and other, peroxides, chlo-.

- rates, perchlorates, persulphates, perborates, etc.,

and/or mixtures thereof, may also be used, with or without air blowing.v

The sulphination products may also be reacted with other organiccompounds to form secondary derivatives. Thus, with alkyl halides toorganic sulphinyl halides react with amines, and

active methylene compounds, etc. These secondary derivatives are, likethe sulphination products themselves, useful as reducing andthesulphinates readily react form sulphones, and the.

"ins a ents of chain saturated aliphatic hydrocarbons have been found toprovide satisfactory, sulphination tions generally described as gas oil'rractions. Paraflin base gas oils, such as are recovered from crudes ofthe Pennsylvania andMichlganflelds,

are particularly desirable, and theindividug] stituents of these gasoils, such as those having especially carbons oi n-tetradecane, verysatisfactory sulphination 'p'roducts for present. purpose. However,either cracked gas oil of paraillnic, naphthenic base or the straightchain saturatedhydrmprocedures before 'sulphinating. For example,

the boiling range of the'gas oil may be narrowed preferably under vacyuum and in the presence of caustic .soda' or other bases. The gas oilmay be given a pre liminary treatment witha small amount of oleum byfractional distillation,

or concentrated sulphuric acid; or the like 'to remove resin-forming andothernnstable, constituents therefrom. It may also be admixed" withfilter clay, silica gel, or decolorizing cal-born;

which materials may be separated therefrom by settling, centrifuging,and/or filtering. A "par ticularly desirable treatment; for obtainingbetter results includes solvent, extraction to remove the more aromaticand/or unsaturated constituents of the gas oil, although the removedconstitu- I hexane," heptadecane, octadecane and hexadecane; petroleumhydrocarbons, including 'paraflln wax, slack. wax, scale wax, Asiaticwax, white oil, kerosene, lubricating oils and railinates of lubricatingoil' and kerosene extractions; hydrocarbons produced by thehydrogenation of oxides of carbon; hydrogenated coal; oleilnes,includingdecene, hexene, cetene and dodecene; tetraisobutylene and otherpolymerized oleflnes; cyclic compounds, including decalin, cyclohexane,methyl 'cyclohexane, dodecyi cyclohexane and cyclohexene; sterols, in-

eluding cholesterol, phytosterol and the like;

resins and fatty acidsand their monohydric and full and partialpolyhydi'ic alcohol esters, includingstearic acid, rosin, spermaceti,tallow, tall oil and monoglycerides of coconut oil; alcohols and theirderivatives; the halogen and other'substituted derivatives of thesematerials, including chlorinated paraiiin wax, chlorinated gas oil,cetyl chloride'and oleilne halides; and various other aliphatic orcycloaliphatic materials andmixtures thereof. It is preferred to treatthe less expensive and more available saturated aliphatic materials.

Where organic carboxylic acids are treated in accordance with thepresentinvention, an amount of thionyl halide suflicientto form the carboxylicacid halide and then to convert this intermediate product tothesulphinyl halide is employed. when alcohols are treated, a suflicientexcess of the present invention, the straight this class, includingn-heptadecane, n-docosane and cetene, provide 2 the mixtures thereo w pT e gas oil or otherpetroleum s be purified or concentrated by -anyofathe imown,

of the saturated or their mixtures, such as a gas oils," are paraiiln'hydrocarbons, including butane, dodecane,

phites and then to'produce sulphinyl halides,

therefrom is used. 4 l The .prmiifs maybe in the form of the acidsproducts. The salts may be interchanged by the treatmentof a solution ofone salt of the novel compounds in a solvent, such as acetone, ethylalcohol, isopropyl alcohol, butyl alcohol, dioxane, monoglycerides,Cellosolve and Carbitol, with a concentrated aqueous solution of asoluble salt of an inorganic acid having a difierent cation from that oftheproduct to be treated. This process also serves to remove'fromtheproduct the-inorganic salts, such as sodium chloride.

The following examples, described herein, are merely illustrative of thepresent invention, and

it will be understood that the invention isnot limited thereto.

Emmple I "About grams of an acid-refined gas oil of paraflinic basehaving a boiling range of about 500 to about 700 F. are mixed with about71 grams of thionyl chloride, and the mixture is placed in a' reactionvessel illuminated by.a 250 watt, type H-2, General Electric mercuryvapor lamp placed about 3 inches away. About '71 grams of gaseouschlorine are slowly passed into the mixture over a period of about sixand onehalf hours. The temperature risesrapidly at first and ismaintained at about 75 C., the color of the mixture remaining a lightyellow during this period. The mixture is thereafter heated to about 115C. and blown with nitrogen to expel unreacted thionyl chloride. Aqueoussodium hydroxide is then added, and the mixture is heated, causing avery vigorous hydrolysis to take place. The mixture is extractedwithgasoline to remove unsaponiflable material therefrom. A quantity ofbenzol'is then added, and the mixture is refluxed, usinga trap to removewater from the condensate before returning it to the distillationvessel, wherebyinorganic salts are precipitated. After decanting, thebenzol is removed by distillation, leaving an amorphous product.- Theproduct is readily soluble in water, and even dilute solutions showunusual foaming and detergent properties. l

Example II About 84 grams of cyciohexane are mixed with about 119 gramsofthionyl chloride in a glass vessel. The mixture is treated with about35 grams of gaseous chlorine'overa period of about two and one-halfhours, while exposed to a mercury-arc lamp. Excess gases areblown outofthe reaction mixture with carbon dioxide, and the mixture is distilledin glass apparatus. The material is heated to about C. under40millimeters of mercury absolute pressure, :and thionyl chloride andunreacted cyclohexane are thereby removed. The distillation temperature1 is then raised, collecting a'minor fraction between about C., thefraction largely com and about prising chloroyclohexane. The system isfurther evacuated to'about*3 to about 4 millimeters of mercury pressure,and the temperature isincreased.) Amajorfraction,

and about C, is collected,=a last fraction between about 110- andabout:1l5 C. showing' boiling between about i signs of decomposition. Themajor fraction oomprises cyclohexyl sulphinyl chloride, a light yellowoil with a characteristic" odor. A portion of this product is hydrolyzedwith sodium on cooling, is crystallized out in flat, shiny flakes.Another portion of the product comprising cyclohexyl sulphinyl chloridedecolorizes dilute potassium permanganate, dilute aqueous iodine and 10a carbon tetrachloride is not decolorized.

The cyclohexyl sulphinyl chloride reacts violently with sodium peroxide,being neutralized and oxidized to form the sodium sulphonateb The sodiumsalt of the sulphonated product is readily soluble in water and inalkaline solutions and has excellent detergent, wetting, emulsifying andfoaming properties.

, Example III from'the vessel Provides illumination to catalyze g thereaction. The mineral oil and the thionyl chloride are precooled, and atemperature of about 10, to about +10 C. is maintained throughout theentire run. When about 35 grams of chlorine have been added, about gramsmore of precooled thionyl chloride areadded, and the chlorine additionis continued until about 35 grams more are consumed At the end of threehours, carbon dioxide is bubbled throughthe reaction mass to sweep outexcess gases, a'nda crude product containingsulphinyl chlorides isobtained as detailed in the preceding examples. Upon hydrolysis with a5% solution of sodium hydroxide, a vigorous reaction ensues, and thesodium salts of the mineral oil sulphinic acids are obtained. The sodiumsalts are isolated from the aqueous solution by a'benzol boiling, as in45 Example I. .r

Example IV I vessel containing transparent beads, and abcutf'l part ofchlorine gas is slowly bubbled into the vessel in countercurrent to thedown-flowing liquids; The mineral oil and the thionyl chloride are pie;55 heated to an extent .suflicient to maintain a tem: perature' of about45 to about 65. C. in the reace, tion vessel, and a mercuryvapor lampabout,,3, inches from the vessel provides a source of actinic light. Amixture of the sulphinyl chloride 60 uct, chlorinated oil; unreactedoil, and excess thionyl chloride is withdrawn atthe bottom of the vesseland passed to the central portion ofan ex; traction column. A volume ofliquid sulphur di oxide about twice that ofthe mixture-is fed into 65the column at the top. I OXlde dissolves the reaction product andwexcessthionyl chloride and is removed at the bottom of; thecolumn, whileunreacted and/or merely chlo-, rinated oil is taken; oil at thetop.Thesulphur; 7o dioxide solution is then-subjected to, vacuum di's:-.

tillation, maintainingma "vacuuminches, and the sulphurdioxide andchloride are separately condensed for reuse... The sulphinylchloride andrecovered hydroxide and,'

aqueous brominesolutions. Bromine dissolved in About 242 grams of aPennsylvania white mineral oil are mixed with about 120 grams of'thionyl weight of a Pennsylvania white he: I liquid sulphur of about 28-excessthionyl reaction prod;

' About 219 creamer lcuroyl chloride ore so A with about 119 ore oftbionyl chloride in e. g ycsseLeud about 85 w of c or into the mixture de period or hours. reaction mixture is expo to lit :frome mercury arc 1pthroughout the reele tiou. The mixture is distilled at about 126 Q underan absolute pressure or w-- of mercury, while n u, s -z,. tllerethrougb.Excess doses and t mm c are thereby removed. The residue cont u reactedluuroyl chloride d lsyl culori lsulplilnyl chloride is hydrolyzed d l-swith sodium hydroxide, and u sure or. owuen is then bubbled tlu-ousbthe material to the sulphlndted' product to the M1; colt or s ulphonotcdleuric acid. This lodllotis ud= 31d; with sodium lute food from notedlauroyl chloride. A portion of issepereted from inorganic suits by theprocedure described in Example I. other portion cl time product isselted out to yield a sub n: free teriel.

I Example yr About low r: w: of cyclolieue are to ;.:-;i u reaction tuwi about 292 u or oil tblcnyl chloride, and menus for melntai the truture of the reaction mixture at about it" to r at" G, are provided. Ageneral Electric t m. 2 ercury vapor lamp located at e tunce or about 3inches from the tube is employed to illuminate the mixture, and aboutgrams of chlorine ere bubbled in throughs iritted g1 res distributorover a period of about two hours. At the eudof this time, the lamp isturned ofi and the ture is blown with carbon dioxide gas to sweep outhydrogen chloride and unreacted chlorine. The reaction mixture is heatedto about now to about 110 C, under on absolute pressure of about 250millimeters of mercury and in at carbon, dlomde atmosphere, 0.distillate being collected which {smells strongly of thionyl chlorideand which also contains a major part of the unreccted cyclolhexane. Theresidue is distilled in vacuo at o 1926881118 01 about 1 to about 2millimeters oi merlmufy. and a fraction boiling between about 60 andabout C. is recovered.

About 5 grams of this lractionis treated with about 6 cc. of 5N sodiumhydroxide. A vigorous reaction ensues. resulting in the formation of amass or colorless crystals. The crystals are washed with ether, filteredand dried. About 2.38

grams of sold crystals are then boiled for about my; hours in an-butanol with about 2.11 grams of m-nitrobenzyl bromide. The reactionmixture is then filtered, and the filtrate is allowed to cool. Qrystals'are obtained which are then taken up with ethanol and are recrystallizedtherefrom, the gylsggllile product melting sharply at about 1'16-.';la.ra-nitrobenzyl cyclohexyl sulphone is then ll reporedsynthetlcsllylnthc {allowing manner:

About 13.5 grams or magnesium turning; are

created with about 82.5 cc. of cyclohexyl bromide tn about 250 cc. ofdry othcrto make a Grisnard moo-gent. About cc; 0! liquid sulphurdioxide dissolved in about 200 cc. 0! ether-ore then added thereto.- Asolid separates during the addition and is redissolved in excess sulphurdioxide-ether solutlon. The mixture is thereafter poured up n rushedice. and magnesium carbonate is added with ut 2.35

' ntal cyclum 5 with the collide pruct;

11.:- obtained by llting about 3- sror sodium in; w evil: whereupon eeris added to the solution. Fine white leaflets oi the sodium sulpete aretliero by caused to seperotc. and these are put in a or bromide, end ubuteuol. e :o 1.: we is refluxed for about due bouro d is en filte bot.trate is allowed too, cud

bone cote thereirom -csc oiu token up with col dud use recryst Thtols'tnus obtained ore found to melt r .t; about 176 to 377 C A ixtureorthese l med by the treatment or cyclolieo with onyl coridc cud ueut Mtlou reectloth p nltrobol br 1 all also melts on M cyclones withtbiou'yl oycloheuyl sulpl c e, which, drolysis and ueutmlicetion to sumdro ide, yields cyclolieuyl sulpc ucld w: cult.

imilerly, smetricsl di-cyclohewlsulpbouylw is synthetior, pre

d'reection and is com a"; by means of the cycioheuyl culphincte prepdthe p -w -r of this invention with about doc, of ethylene bromidc. Eachstslline product, as well a mixture of the two, melts at about Q.

The sulpllinate and sulpbonste products obnod eccorg to the presentinvention aye good wet. sombmun date water -soltcuing, "-11.

. s. trstiuucnd equalizing properti Althoughthese products mayadvantageously be used in hard as well as in solt water, whether hot orcold, and

in the presence or absence of large quontitico of inorganic salts, suchas sodium chloride dium sulphate, it is generally preferred to employthe sulphonste products for use in hard water.

ethanolamlne and triothanolamine and their sows: alkaline soap bmlders,water softeners, and othersalts including box-ax, sodium carbonate,diluted-phosphates, tctrapliospbate. pyrophosphate, hexamctaphosphatc.sulphate. chloride. acetate, citrate, tcrtrste, bicarbonate,aeoqulcsrboncte. thiosulphotc, 1nd hydrosulphite,

and their other alkali, metal, ammonia, and amine salts or alkyl esters;aolds,'includinz borlc sold, citric cold cud tartaric acid; coloring mattor, including dyes.,lnkcs. plsments; sbnslves and tillers, includingsilica, pumice, feldspar. precipitated chalk, ini'usorislourthrbcntonltc,

talc, starch, and oil; liquids; including carbon. tetrachloridepcrchlorctbylene, trichlorethylen j 76 slycerine, ethyl alcoh l.tctrsbydrolurturyl olcolcrless leaflets of.

sitions; rug cleaners;

depend, of course, upon the ultimate use of the new compositions.

The final composition, with or without one or more addition agents, maybe formed into beads, flakes, bars, chips, crystals, powders, so-

lutions, liquid or plastic emulsions, pastes,

water, tetralin,

creams, salves, or any other formsdesired. The

ingredients may methods, such as grinding, stirring, kneading,crutching, fusing, and drying of mixed solutions or dispersions byheated rolls, sprayingor other means.

The various products and compositions of this invention may be used forvarious purposes, such as laundry detergents and other textile agentsincluding laundry blueing, bleaching, dyeing, .mercerizing, softening,lubricating, and discharging compositions; drain, lavatory and radiatorcleaners; anti-oxidants for soaps and other compositions; reducingagents; paint, stain and grease removers; dry-cleaning compowatersofteners; washing compositions for fruit, fabric, wood, metal, stone,glass, brick, masonry, and alkali sensitive and/or painted surfaces;liquid, solid and paste tooth and mouth detergents; shampoos; cosmetics;depilatories; deodorants and perfumes; antiseptics; insecticides;dust-preventing compositions; fire extinguishing compositions;-anti-freezing, anti-fogging, and anti-corrosion compositions; woodimpregnants; electrolytic baths; metal plating; metal pickling; etchingcompositions; tanning agents. and fat-liquors for leather; photographicsolutions; petroleum de-emulsifying compositions; lubricating oil andfuel composiore flotation; fat splitting; cements and be mixed by any ofthe commonabrasive compositions;

scope of. the present purview of the appended claims.

I claim:

1. The process of preparing sulphinic derivatives of proportion of ahalogen in the presence of actinic rays.

2. The process of preparing sulphiniclderivatives of organic compoundswhich comprises an organic compound having an aliphatic group withthionyl bromide and a minor proportion of a halogen in the presence ofactinic light.

3. The process of tives of organic compounds which comprises treating anorganic compound having an aliphatic thionyl chloride and a minorproportion of chicrine in the presence of actinic light.

ganic sulphinyl halides, and removing said organic sulphinyl halideswith a selective solvent therefor.

7. The process of preparing sulphonic derivatives of organic compoundsspecification and within the preparing sulphinic deriva- I -a halogen inthe presence tives of organic compounds which comprises treating anorganic alip atic compound having about twelve to about twenty carbonatoms with thionyl chloride and a minor proportional a halogen in thepresence of actinic light and at a temperature of about -10 to about200! C.

actinic light and a temperature of about 25 to about 100 C. toitormorganic sulphinylchlorides,

:and hydrolyzingand neutralizing said organic sulphinyl chlorides withan alkaline material.

15. The process of preparing organic, 'sul phonates. which comprisestreating an organic aliphatic compound having abouttwelve to abouttwenty carbonatomsw'ith fthionyl chloride and, chlorine in thepresence'of actinic light and at a 1 14. The process of preparingorganic sulphinates which comprises treating an organic aliphaticcompound having about twelveto about twenty carbon atoms with thionylchloride and a minor proportion of chlorine in the presence of tralizingsaid organic temperature of about 253 to about 100 C. to form organicsulphinyl chlorides, hydrolyzing and neusulphinyl chlorides with analkaline materialto form organic sulphinates and oxidizing said organicsulphinates.

DWIGHT JAMES Po'rrim.

